Synthesis, Structures, and Electronic Properties of 2,7-Anthrylene-Based Azacyclophanes Bearing <i>o</i>-, <i>m</i>-, and <i>p</i>-Phenylenediamine Linkers
Synthesis, Structures, and Electronic Properties of 2,7-Anthrylene-Based Azacyclophanes Bearing <i>o</i>-, <i>m</i>-, and <i>p</i>-Phenylenediamine Linkers
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带有<i>o</i>-、<i>m</i>-和<i>p</i>-苯二胺连接基的2,7-蒽基氮杂环芳烃的合成、结构和电子性质
DOI：
10.1021/acs.joc.1c00856
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Toyota Shinji
中科院分区：
文献类型：
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作者：
Iwanaga Tetsuo;Komori Takashi;Sato Hiroki;Suzuki Shuichi;Yamauchi Tomokazu;Misaki Yohji;Sato Hiroyasu;Toyota Shinji
通过Buchwald-Hartwig偶联反应，设计并合成了一系列由2，7-蒽烯和亚苯基结构单元组成的新型氮杂环蕃化合物，研究了它们在多氧化态下的独特电子性质.循环伏安法表明，对苯撑衍生物呈现3个可逆氧化波，邻苯撑和间苯撑衍生物呈现2个准可逆氧化波，这是由于氧化单元与中性单元之间存在复杂的分子内相互作用。不同氧化态的对苯撑衍生物的吸收光谱在865和1025 nm处有明显的吸收带，这是分子内电荷转移作用的结果。对苯撑类似物的电物理和电化学性质也进行了比较，那些邻，间苯撑衍生物的基础上进一步评估的分子内电子相互作用的理论计算。
A series of novel azacyclophanes consisting of 2,7-anthrylene and phenylene units were designed and synthesized by the Buchwald–Hartwig coupling reaction to investigate their unique electronic properties in multiple oxidized states. Cyclic voltammetry showed that thep-phenylene derivative exhibited three reversible oxidation waves, whereas theo- andm-phenylene derivatives showed two quasi-reversible oxidation waves due to the complicated intramolecular interaction between the oxidized units and neutral units. Moreover, the absorption spectra of thep-phenylene derivative in different oxidation states showed absorption bands at 865 and 1025 nm, which were attributed to intramolecular charge–transfer interactions. The photophysical and electrochemical properties of thep-phenylene analog were also compared with those of theo- andm-phenylene derivatives based on theoretical calculations for further evaluation of the intramolecular electronic interactions.